TW201602267A - Active energy beam-curable resin composition, resin molding, and method for producing resin molding - Google Patents

Abstract

A resin composition with which it is possible to form a cured film having excellent weather resistance and wear resistance; and a resin molding having said cured film. An active energy beam-curable resin composition containing a radical polymerizable compound and a photopolymerization initiator (d), wherein said radical polymerizable compound contains 57-90 mass% of (a) caprolactone-modified mono- or poly-penta erythritol poly (meth)acrylate represented by formula (1) and 10-43 mass% of (b) urethane (meth)acrylate synthesized from a polycarbonate polyol having a branched alkyl structure and an average molecular weight falling within the range of 500-1000, a diisocyanate having an alicyclic structure, and a mono (meth)acrylate containing a hydroxyl group. In formula (1), each X independently represents a caprolactone-modified (meth)acryloyl group, a (meth)acryloyloxy group, or a -OH group.

Description

Active energy ray-curable resin composition, resin molded article, and resin molding Product manufacturing method

The present invention relates to a resin composition which can be cured by irradiation with an active energy ray and can form a cured film on the surface of a substrate such as a resin molded article. Further, the present invention relates to a resin molded article in which the cured film is formed, and a method of producing the resin molded article.

A resin molded article made of a polymethyl methacrylate resin, a polymethacrylimide resin, a polycarbonate resin, a polystyrene resin, an acrylonitrile styrene resin, or the like is not only lightweight but also excellent in impact resistance, and Transparency is also good. These resins are materials used for various members such as lamp lenses, glazings, and watch-type protective layers for automobiles. In particular, a headlamp lens for an automobile uses a resin molded article in order to cope with the weight reduction of the automobile and the diversification of the design. However, since the resin molded article is insufficient in abrasion resistance, it is likely to be damaged on the surface due to contact with other hard objects, friction, scratching, etc., and damage to the surface may lower the commercial value. In addition, weather resistance is also an important performance for automotive components. In particular, polycarbonate resins are less resistant to weathering, yellowing due to ultraviolet light, or resin A crack occurs on the surface of the molded article.

As a method of improving the defects of the resin molded article, a method of applying a resin composition containing a radical polymerizable compound and irradiating an active energy ray to form a cured film is disclosed (Patent Documents 1 to 6). Further, it is known that a laminate having a resin layer which is a (meth) material containing a polycarbonate polyol having a branched alkyl structure as a raw material, is excellent in strength and elongation in a tensile test. The composition of the urethane urethane compound is irradiated with an active energy ray to cure the composition (Patent Document 7).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 56-122840

[Patent Document 2] Japanese Patent Laid-Open No. 05-230397

[Patent Document 3] Japanese Patent Laid-Open No. 06-128502

[Patent Document 4] Japanese Patent Laid-Open No. Hei 05-179157

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2000-63701

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2002-348499

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2007-30479

However, the hardness obtained from the previous active energy ray-curable resin composition The film has insufficient wear resistance and weather resistance. An object of the present invention is to provide an active energy ray-curable resin composition which can form a cured film having excellent weather resistance and abrasion resistance, a resin molded article in which a cured film obtained by curing the resin composition is formed, and A method of producing the resin molded article.

The above problem can be solved by any one of the following [1] to [9] of the present invention.

[1] An active energy ray-curable resin composition comprising a radically polymerizable compound and a photopolymerizable initiator (d), and the radical polymerizable compound is based on 100% by mass of the total amount, and includes The poly(meth)acrylate of the mono- or polypentaerythritol modified by the caprolactone represented by the following formula (1) (a) 57% by mass to 90% by mass and the (meth)acrylic acid urethane ( b) 10% by mass to 43% by mass, the (meth)acrylic acid urethane (b) is a polycarbonate polyol having a branched alkyl structure and having a number average molecular weight of 500 to 1,000, A diisocyanate having an alicyclic structure and a mono(meth)acrylate having a hydroxyl group are synthesized.

In the formula (1), "4+2n" X are each independently a modified group of (meth)acryl oxime (which is (CH ₂ =CR-CO(O(CH ₂ ) ₅ C=O) _y -, Its modified source is its own lactone, R represents hydrogen or methyl, y represents an integer of 1 or more and 5 or less, (meth) propylene oxime (CH ₂ =CR-COO-), and R represents hydrogen or methyl. Or an -OH group, at least one X is a modified group of (meth)acryl oxime, at least two X are (meth) propylene fluorenyl groups, and the remaining X is an -OH group. In addition, n is an integer of 0 to 4.

[2] The active energy ray-curable resin composition according to the above [1], wherein the radical polymerizable compound further contains a radical polymerizable monomer (c) 7 based on 100% by mass of the total amount. 5% by mass or less, the radical polymerizable monomer is a radical polymerizable property other than the above-mentioned mono or polypentaerythritol (meth) acrylate (a) and the above (meth) acrylate urethane (b) Monomer and crystallized at a temperature of 25 °C.

[3] The active energy ray-curable resin composition according to the above [1] or [2], wherein the ultraviolet absorbing agent (e) 0.5 mass is further contained in an amount of 100 parts by mass based on the total amount of the radical polymerizable compound. ~20 parts by mass.

[4] The active energy ray-curable resin composition according to the above [3], wherein the ultraviolet ray absorbing agent (e) has a molecular weight of 500 or more.

[5] The active energy ray-curable resin composition according to the above [3], wherein the ultraviolet absorber (e) is a combination of two or more ultraviolet absorbers having a molecular weight of 500 or more.

[6] The active energy ray-curable resin composition according to any one of the above [1] to [5], wherein the hindered amine light is further contained in an amount of 100 parts by mass based on the total amount of the radical polymerizable compound. The stabilizer (f) is 0.1 part by mass to 5 parts by mass.

[7] A resin molded article obtained by curing the active energy ray-curable resin composition according to any one of the above [1] to [6], wherein a hardened film is formed on the surface thereof.

[8] The resin molded article according to the above [7], wherein the resin molded article is an automotive headlamp lens.

The method of producing a resin molded article according to any one of the above [1] to [6], wherein the active energy ray-curable resin composition according to any one of the above [1] to [6] is coated with The surface of the resin molded article is laid, and the obtained coating film is irradiated with an active energy ray.

The active energy ray-curable resin composition of the present invention can form a cured film excellent in weather resistance and abrasion resistance. The resin molded article of the present invention is excellent in weather resistance and abrasion resistance. According to the method for producing a resin molded article of the present invention, a resin molded article excellent in weather resistance and abrasion resistance can be obtained.

First, each component of the resin composition of the present invention will be described. In the following description, the poly(meth)acrylate (a), the (meth)acrylic acid urethane (b), and the radical polymerizable monomer (c) of the above mono or polypentaerythritol are used. The photopolymerization initiator (d), the ultraviolet absorber (e), and the hindered amine light stabilizer (f) are respectively referred to as (a) component, (b) component, (c) component, and (d) component. , (e) component, and (f) component. Further, in the present invention, "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)acryloyl group means "acryloyl group" Or "methacryloyloxy", "(meth)acryloyloxy" means "acryloxy" or "methacryloxy".

<(a) component>

The active energy ray-curable resin composition of the present invention contains the caprolactone-modified mono- or polypentaerythritol poly(meth) acrylate (a) represented by the above formula (1) as a radical polymerizable compound.

By using the component (a), the resin composition exhibits a good polymerization activity by irradiation with an active energy ray, and a polymer having a high crosslinking density and excellent abrasion resistance can be produced. Therefore, a hardened film excellent in abrasion resistance can be formed on the surface of the substrate.

Specific examples of the component (a) include compounds in which the (meth)acryloyl group in the mono- or polypentaerythritol poly(meth)acrylate is modified with the source caprolactone. Examples of the poly(meth)acrylate of pentaerythritol include the following. Tris(meth) acrylate of pentaerythritol, tetra (meth) acrylate of pentaerythritol, tri (meth) acrylate of dipentaerythritol, tetra (meth) acrylate of dipentaerythritol, and penta (methyl) of dipentaerythritol Acrylate, hexa(meth) acrylate of dipentaerythritol, tetra (meth) acrylate of tripentaerythritol, penta (meth) acrylate of tripentaerythritol, hexa(meth) acrylate of tripentaerythritol, triptite Hexa (meth) acrylate and octa (meth) acrylate of tripentaerythritol. Here, as the poly(meth)acrylate of the mono- or polypentaerythritol, from the viewpoint of the weather resistance of the cured film, poly(pentaerythritol) poly(meth)acrylate, more preferably dipentaerythritol, is preferable. (Meth) acrylate. As the poly(meth)acrylate of dipentaerythritol, from the viewpoint of weather resistance of the cured film, penta(meth)acrylate of dipentaerythritol and hexa(meth)acrylate of dipentaerythritol are preferable. VIII (meth)acrylic acid of dipentaerythritol ester. Further, as the poly(meth)acrylate of mono or polypentaerythritol, from the viewpoint of curability, a polyacrylate of mono or polypentaerythritol is preferred.

In the formula (1), the (meth)acryloyl group (CH ₂ =CR-CO(O(CH ₂ ) ₅ C) modified with the source caprolactone from the viewpoint of the abrasion resistance of the cured film _{y of y} -) is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1. In addition, the number of (meth) acrylonitrile groups modified by the source lactone is 1 or more and "2n + 2" or less in terms of the average number of each molecule of the component (a), and the lower limit is hardened. From the viewpoint of weather resistance of the film, it is preferably 2 or more. Further, the upper limit thereof is preferably "2n+1", more preferably 2n, from the viewpoint of scratch resistance and yellowing degree of the cured film.

In the resin composition of the present invention, the amount of the component (a) is from 57% by mass to 90% by mass based on 100% by mass of the total of the radical polymerizable compound. The lower limit of the range is preferably 65 mass% or more, and more preferably 71 mass% or more. Further, the upper limit of the range is preferably 85% by mass or less, and more preferably 80% by mass or less. The more the amount of the component (a) is formulated, the higher the abrasion resistance of the cured film. Further, the smaller the amount of the component (a), the higher the weather resistance and heat resistance of the cured film.

<(b) component>

The active energy ray-curable resin composition of the present invention contains (meth)acrylic acid urethane (b) as a radical polymerizable compound, and the (meth)acrylic acid urethane (b) is branched Polycarbonate polyol (b1) having an alkyl group structure and having a number average molecular weight of 500 to 1000, a diisocyanate having an alicyclic structure (b2), and a mono(meth)acrylate having a hydroxyl group (b3) Synthesized. By using the component (b), it is possible to impart toughness to the cured film of the resin composition, and to improve the weather resistance of the cured film.

The first raw material of the component (b), that is, the polycarbonate polyol (b1) has a branched alkyl structure. By the raw material of (b1), even when the concentration of the solid content component is high, the storage stability of the resin composition is improved, and the flexibility of the cured film obtained from the resin composition is improved. The polycarbonate polyol has a number average molecular weight of from 500 to 1,000. When the number average molecular weight is 500 or more, the weather resistance of the cured film obtained from the resin composition is improved. Further, by setting the number average molecular weight to 1,000 or less, the abrasion resistance of the cured film is improved. Further, the number average molecular weight can be calculated from the following formula from the hydroxyl value and the number of hydroxyl groups in one molecule of the alcohol as a constituent component of the polycarbonate polyol.

Number average molecular weight = (56.11 × N / [hydroxy value]) × 1000

Here, N represents the number of hydroxyl groups contained in one molecule of the alcohol component.

Such a polycarbonate polyol can be synthesized, for example, by transesterification of a polyol having a branched alkyl structure with a carbonate.

The polyol having a branched alkyl structure is preferably a glycol from the viewpoint of reactivity of transesterification. The branched chain alkyl structure of the polyol is preferably a structure having a side chain of a linear alkyl group in the main chain of the linear alkyl group from the viewpoint of reactivity of the transesterification. The carbon number of the main chain of the branched alkyl structure is preferably from 3 to 15, more preferably from 5 to 8, from the viewpoint of the scratch resistance of the cured film. Further, the carbon number of the side chain of the branched alkyl structure is preferably from 1 to 10, more preferably from 1 to 3, from the viewpoint of reactivity. Preferable specific examples of the polyhydric alcohol having a branched alkyl structure include 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, and 2 -Methyl-1,8-octanediol and the like.

The following are mentioned as a carbonate. a cyclic carbonate such as ethylene carbonate; a dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, dibutyl carbonate or dicyclohexyl carbonate; a diaryl carbonate such as diphenyl carbonate; . The carbonate is preferably a dialkyl carbonate from the viewpoint of weather resistance of the cured film.

Commercially available products can also be used as the polycarbonate polyol. Specifically, as a commercial item of a polycarbonate polyol having a branched alkyl structure and having a number average molecular weight of 500 to 1,000, for example, the following may be mentioned. KURARAY POLYOL C-590 (quantitative average molecular weight 500), KURARAY POLYOL C-770 (quantitative average molecular weight 800), KURARAY POLYOL C-1050 (quantitative average molecular weight 1000), KURARAY POLYOL manufactured by KURARAY Co., Ltd. C-1090 (number average molecular weight: 1000), KURARAY POLYOL C1065N (number average molecular weight: 1000), KURARAY POLYOL C-1015N (number average molecular weight: 1,000), and the like.

The second raw material of the component (b), the diisocyanate (b2), has an alicyclic structure. The cured film obtained from the resin composition is excellent in both weather resistance and abrasion resistance by the raw material (b2). The diisocyanate is preferably dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane-2,4-diisocyanate or methylcyclohexane from the viewpoint of weather resistance of the cured film. a diisocyanate having a cyclohexane structure such as 2,6-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane or isophorone diisocyanate.

The third raw material of the component (b), that is, the mono(meth)acrylate (b3) having a hydroxyl group, is a compound having one (meth)acryloyl group in one molecule. The softness of the cured film obtained from the resin composition is improved by the raw material (b3). In addition, in contrast to the case of (meth) acrylate having two or more (meth) acrylonitrile groups in one molecule The storage stability of the resin composition and the cured film obtained from the resin composition are excellent in weather resistance. Specific examples of the mono(meth)acrylate include the following. Hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate; butyl glycidyl ether, 2 - an addition reaction of a monoepoxy compound such as ethylhexyl glycidyl ether with (meth)acrylic acid; a mono(meth)acrylate of polyethylene glycol or polypropylene glycol; a single (poly) of polycaprolactone diol Base) acrylate and the like. From the viewpoint of the scratch resistance of the cured film, a hydroxyalkyl (meth) acrylate is preferred, and a hydroxyalkyl group preferably has a carbon number of 2 to 4, particularly preferably (meth)acrylic acid 2 - hydroxyethyl ester.

The method for producing the component (b) is, for example, a method in which the above three raw materials are reacted in the presence of a catalyst which reacts an isocyanate group with a hydroxyl group to form a urethane bond. The mixing ratio of the three raw materials is preferably such that the isocyanate group and the hydroxyl group are substantially equal to the molar amount from the viewpoint of stable production of the reactant. The reaction temperature of the urethanization reaction is preferably from 60 ° C to 70 ° C, and the reaction time is preferably from 1 hour to 20 hours. The catalyst is preferably di-n-butyltin dilaurate. In general, since the reactant is highly viscous, it is preferred to dilute it with an organic solvent or other diluent monomer during or after the reaction.

The amount of the component (b) in the resin composition of the present invention is 10% by mass to 43% by mass based on 100% by mass of the total of the radical polymerizable compound. Further, the lower limit of the range is preferably 15% by mass or more, and the upper limit is preferably 29% by mass or less. The more the blending amount of the component (b), the higher the weather resistance of the cured film and the hardenability of the resin composition in the air environment, and the less the blending amount of the component (b), the abrasion resistance of the cured film The more the sex is improved.

<(c) component>

In the active energy ray-curable resin composition of the present invention, the radical polymerizable compound may contain the component (c) as an optional component in addition to the components (a) and (b), and the component (c). It is a radically polymerizable monomer other than the component (a) and (b), and is crystallized at a temperature of 25 °C. The presence or absence of crystallization at a temperature of 25 ° C can be determined by the following method. Specifically, the appearance of the compound after storage for 10 days at a temperature of 25 ° C was visually evaluated to determine the presence or absence of a crystal component.

The amount of the component (c) in the resin composition is preferably 7% by mass or less, more preferably 5% by mass or less, and still more preferably 3 mass% based on 100% by mass of the total of the radical polymerizable compound. % or less is particularly preferably 1% by mass or less, and most preferably 0% by mass. By reducing the blending amount of the component (c), even when the concentration of the solid content component of the resin composition is high, the storage stability of the resin composition is improved.

Specific examples of the component (c) include the following. Hydroxyethyl bis(2-propenyloxyethyl) isocyanurate, tris(2-propenyloxyethyl) isocyanurate, bis(2-propenyloxypropane) Isocyanurate such as ester hydroxyethyl ester or tris(2-propenyl methoxypropyl) isocyanurate; further, stearyl acrylate, 1-adamantyl acrylate, pentaerythritol tetraacrylate, etc. .

<(d) component>

The photopolymerizable initiator (d) is a compound which can initiate polymerization of a (meth)acrylic monomer or oligomer by irradiation of an active energy ray.

Specific examples of the component (d) include the following. Benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzoin, benzophenone, p-methoxydiphenyl Methyl ketone, diethoxyacetophenone, benzoin dimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methyl benzoic acid methyl ester, benzo Ethyl phthalate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propenyl) a carbonyl compound such as -benzyl}-phenyl]-2-methyl-propan-1-one; a sulfur compound such as tetramethylthiuram monosulfide or tetramethylthiuram disulfide; 2,4,6- A fluorenylphosphine oxide such as trimethylbenzhydryldiphenylphosphine oxide. These are used singly or in combination of two or more. Among these, benzophenone, benzoin isopropyl ether, methyl benzoic acid methyl ester, and benzoin dimethyl ketal are more preferable.

The amount of the component (d) in the resin composition of the present invention is preferably from 0.1 part by mass to 10 parts by mass per 100 parts by mass of the total amount of the radically polymerizable compound. Further, the lower limit of the range is more preferably 1 part by mass or more, and the upper limit is more preferably 5 parts by mass or less. The more the amount of the component (d) is, the higher the curability of the resin composition is, and the smaller the amount of the component (d) is, the more the transparency and weather resistance of the cured film are improved.

<(e) component>

The resin composition of the present invention preferably further contains an ultraviolet absorber (e). The component (e) is preferably a molecular weight of 500 or more from the viewpoint of heat resistance of the resin molded article. The (e) component is preferably an ultraviolet absorber which is excellent in solubility in a resin composition and improvement in weather resistance of a resin molded article in which a cured film of a resin composition is formed. The agent is derived from a triazine system, a benzophenone system, a benzotriazole system, a phenyl salicylate system, or a phenyl benzoate compound, and has a maximum absorption wavelength in the range of 240 nm to 380 nm. From the viewpoint of being largely contained in the resin composition, a benzophenone-based ultraviolet absorber is preferred. In addition, it prevents yellowing of a substrate such as polycarbonate. From the viewpoint, a triazine-based or benzotriazole-based ultraviolet absorber is preferred.

Specific examples of the component (e) include the following. 2-[4-{(2-hydroxy-3-dodecyloxy-propyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxy-propyl)oxy}-2-hydroxyphenyl]-4,6-bis (2, 4-dimethylphenyl)-1,3,5-triazine, 2-{4-(2-methylacetate octyl)oxy-2-hydroxyphenyl-4,6-{double (2 a triazine compound such as 4-methylphenyl)}-1,3,5-triazine; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone Equivalent benzophenone compound; 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzo a benzotriazole compound such as triazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol; Phenyl salicylate, p-tert-butylphenyl salicylate, phenyl benzoate such as (1,1,3,3-tetramethylbutyl)phenyl salicylate; phenyl salicylate An ester, a phenyl salicylate compound such as 3-hydroxyphenyl benzoate or resorcinol dibenzoate. In the above, from the viewpoint of obtaining a cured film of a resin composition and obtaining a cured film having a high surface hardness, a triazine-based compound is preferred, and 2-[4-{(2-hydroxy-3-) is more preferred. Dodecyloxy-propyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4 -{(2-hydroxy-3-tridecyloxy-propyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3, 5-triazine.

The component (e) may be used by combining two or more kinds of ultraviolet absorbers having a molecular weight of 500 or more. Particularly, from the viewpoint of the scratch resistance of the cured film, 2-[4-{(2-hydroxy-3-dodecyloxy-propyl)oxy}-2-hydroxyphenyl] is preferred] -4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxy-propyl)oxy A group of 2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine is used in combination.

The amount of the component (e) in the resin composition of the present invention is preferably 0.5 parts by mass to 20 parts by mass based on 100 parts by mass of the total amount of the radically polymerizable compound. Further, the lower limit of the range is more preferably 5 parts by mass or more, and the upper limit is more preferably 15 parts by mass or less. The higher the blending amount of the component (e), the higher the weather resistance of the cured film, and the less the amount of the component (e), the hardenability of the resin composition, the toughness of the cured film, and the heat resistance. The more wear resistance is improved.

<(f) component>

The resin composition of the present invention preferably further contains a hindered amine-based light stabilizer (f). The component (f) is not particularly limited as long as it is a hindered amine light stabilizer. Specific examples of the component (f) include the following. Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate Ester, bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-ethoxy-2,2,6, azelaic acid 6-tetramethyl-4-piperidinyl) bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, azelaic acid bis( 1-butoxy-2,2,6,6-tetramethyl-4-piperidinyl), bis(1-pentyloxy-2,2,6,6-tetramethyl-4) sebacate -piperidinyl)ester, bis(1-hexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-heptyloxy-2) sebacate , 2,6,6-tetramethyl-4-piperidinyl), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, Bis(1-decyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-decyloxy-2,2,6,6- sebacate Tetramethyl-4-piperidinyl), bis(1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, malonic acid bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl)-2-(4-methoxy-benzylidene) ester, 1,2,3,4-butanetetracarboxylic acid Tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl Piperidine derivatives such as 4-piperidinyl) ester ; 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4- a condensate of piperidinol with β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol; , 2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol with β,β,β,β-tetramethyl-3,9-(2, a condensate of 4,8,10-tetraoxaspiro[5,5])undecane)diethanol; anthracene dicarboxylic acid and 2,2,6,6-tetramethyl-1-octyloxy-4 - an amine group-containing compound such as a diester compound of piperidinol, a reaction product of 1,1-dimethylethyl hydroperoxide or octane (manufactured by BASF, trade name TINUVIN 123) . Among them, from the viewpoint of weather resistance of the cured film, a piperidine derivative and a compound containing an aminoether group are preferable, and a bismuth azelaic acid (1,2,2,6,6-penta) is preferred. Di-4-piperidinyl) ester, diester compound of hydrazine dicarboxylic acid and 2,2,6,6-tetramethyl-1-octyloxy-4-piperidinol, hydrogen peroxide 1,1- A reaction product of dimethylethyl and octane.

The amount of the component (f) in the resin composition of the present invention is preferably 0.1 part by mass to 5 parts by mass based on 100 parts by mass of the total amount of the radically polymerizable compound. Further, the lower limit of the range is more preferably 0.3 parts by mass or more, and the upper limit is more preferably 3 parts by mass or less. The more the blending amount of the component (f), the higher the weather resistance of the cured film, and the less the amount of the component (f), the hardenability of the resin composition, the toughness of the cured film, and the heat resistance. The more wear resistance is improved.

Although the components (a) to (f) have been described above, the resin composition of the present invention may further contain an organic solvent, an antioxidant, an anti-yellowing agent, a blueing agent, or the like as needed. Various additives such as pigments, leveling agents, defoamers, tackifiers, anti-settling agents, antistatic agents, antifogging agents, and the like.

The organic solvent is preferably selected depending on the kind of the substrate. For example, when polycarbonate is used as the substrate, an alcohol solvent such as isobutanol or an ester such as n-butyl acetate is preferred. The solvent is used singly or in combination of two or more kinds thereof.

<Resin molded product>

When the resin composition of the present invention is applied onto the surface of a resin molded article as a substrate, and the obtained coating film is irradiated with an active energy ray to form a cured film, a resin excellent in abrasion resistance and weather resistance can be obtained. Molded product. In order to apply the resin composition to the substrate, for example, brush coating, spray coating, dip coating, spin coating, curtain coating may be used. , bar coating and other methods. From the viewpoints of the coatability of the resin composition, the smoothness and uniformity of the coating film, and the adhesion of the cured film to the resin molded article, it is preferred to apply a coating obtained by adding an organic solvent to the resin composition. Cloth liquid. Further, in order to lower the viscosity, the resin composition may be heated or diluted with a subcritical fluid.

The coating film of the resin composition applied onto the resin molded article is irradiated with active energy rays to form a cured film. The film thickness of the coating film formed on the resin molded article is preferably from 1 μm to 50 μm, more preferably from 3 μm to 20 μm. The active energy ray is preferably ultraviolet ray from the viewpoint of good curability of the coating film and productivity of the resin molded article. As the ultraviolet source, a high pressure mercury lamp, a metal halide lamp, or the like can be used. The ultraviolet light is preferably irradiated with ultraviolet rays of 100 nm to 400 nm so as to be 100 mJ/cm ² to 5000 mJ/cm ² . The environment in which the active energy ray is irradiated may be air or an inert gas such as nitrogen or argon.

The resin composition of the present invention can be used for surface modification of various resin molded articles. The material of the resin molded article includes various thermoplastic resins or thermosetting resins. Specifically, polymethyl methacrylate resin, polycarbonate resin, and polyester tree are mentioned. Fat, polyester carbonate resin, polystyrene resin, acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene resin (AS resin), polyamine resin, polyarylate resin, poly A methacrylimide resin, a polyallyl diethylene glycol carbonate resin, or the like. In particular, the polymethyl methacrylate resin, the polycarbonate resin, the polystyrene resin, and the polymethacrylimide resin are excellent in transparency and improved wear resistance, so that the resin composition of the present invention is very effective. . In addition, the resin molded article is a molded article such as a sheet-shaped molded article, a film-form molded article, or various injection-molded articles obtained by molding the resins. The resin composition of the present invention is particularly suitable for surface modification of a resin molded article such as an automotive headlamp lens that is exposed to a severe environment for a long period of time.

[Examples]

Hereinafter, the present invention will be further described in detail by explaining the examples and comparative examples. The measurement evaluation in the examples was carried out by the following method.

(1) Storage stability

The uncured resin composition was placed in a light-shielded glass bottle and kneaded, and stored at -20 ° C for 1 month. Thereafter, the temperature of the resin composition was returned to room temperature, and the state of the resin composition was visually observed. The resin composition in which any of the foreign matter, the whitening, and the stain were not observed in the resin composition was judged to be "good", and the resin composition of any of the above was judged as "poor".

(2) Abrasion resistance

For the resin molded article having a hardened film formed on the surface thereof, a haze meter (HM-65W, manufactured by Murakami Color Research Co., Ltd.) was used to measure the haze value before and after the abrasion resistance test. The amount of increase in haze value. The abrasion resistance test is based on JIS K7204 "Test method for plastic abrasion by plastic-wear wheel", using ROTARY ABRASION TESTER (manufactured by Toyo Seiki Co., Ltd.) with wear wheel CS-10F and load 4.9N ( 500 gf) 100 times of abrasion test on the hardened film. The abrasion resistance was judged based on the following criteria.

"Excellent": The increase in the haze value is 0% or more and less than 5%.

"Good": The increase in the haze value is 5% or more and less than 10%.

"Poor": The increase in haze value is 10% or more.

(3) Weather resistance

A resin molded article having a hardened film formed on its surface is weather resistant using a sunlight carbon weather meter (SUGA TEST INSTRUMENTS Co., Ltd., model WELSUN-HC-B). The test machine was subjected to a 4000-hour weather resistance test under the conditions of a black panel temperature of 63 ± 3 ° C, a rainfall of 12 minutes, and a cycle of irradiation for 48 minutes. Then, the following evaluations (A) to (C) were performed.

(A) appearance

After the weather resistance test, the appearance of the cured film was visually observed. The cured film of any one of the hardened film, which is not cracked, whitened, stained, or cured, is judged as "good", and the cured film which is one of the above is judged as "bad". .

(B) Transparency

The haze value before and after the weather resistance test of the resin molded article was measured using a haze meter (HM-65W, manufactured by Murakami Color Research Laboratory Co., Ltd.), and the amount of increase in the haze value was calculated and determined based on the following criteria.

"Excellent": The increase in the haze value is 0% or more and less than 2.0%.

"Good": The increase in the haze value is 2.0% or more and less than 5.0%.

"Poor": The increase in the haze value is 5.0% or more.

(C) yellowing degree

The ultraviolet index (YI, Yellow Index) before and after the weather resistance test of the resin molded article was measured using an ultraviolet and visible spectrophotometer (trade name: INTENSIFIED MULTICHANNEL PHOTODETECTOR MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). The value is calculated as the amount of increase in the YI value. Further, the YI value was measured by measuring the tristimulus values (X, Y, and Z) and using the following formula.

YI value = 100 × (1.28 × X - 1.06 × Z) / Y

The amount of increase in the YI value is determined based on the following criteria.

"Excellent": The increase in the YI value is 0 or more and less than 1.0.

"Good": The increase in the YI value is 1.0 or more and less than 5.0.

"Poor": The increase in the YI value is 5.0 or more.

(4) Heat resistance

The heat resistance test was carried out by placing a resin molded article having a cured film formed on its surface in a dryer at 120 ° C for 480 hours. After the resin molded article was taken out from the dryer, the cured film was visually observed, and those who did not observe the crack were judged as "good", and those who observed the crack were judged as "poor".

[Synthesis Example 1 (synthesis of UA1)]

Adding dicyclohexylmethane as diisocyanate to a 5 L flask equipped with a dropping funnel with a heat retention function, a reflux cooler, a stirring blade and a temperature sensor -4,4'-diisocyanate 2 mol, n-butyltin dilaurate 300 ppm, and the flask was warmed to 40 ° C in a warm water bath. In the state where the dropping funnel with the heat insulating function was heated to 40 ° C, it took 4 hours to use a polycarbonate diol having a 3-methylpentane structure as a diol (a number average molecular weight of 800, KURARAY) Manufactured by the company, trade name KURARAY POLYOL C770) 1 moles were added to the above flask. The liquid in the flask was stirred at 40 ° C for 2 hours, and further heated to 70 ° C for 1 hour. Thereafter, 2 ml of 2-hydroxyethyl acrylate having a hydroxyl group-containing mono(meth)acrylate was added to the flask over 2 hours, and the liquid in the flask was further stirred for 2 hours to synthesize an amide. Carbamate UA1 (hereinafter abbreviated as "UA1").

[Synthesis Example 2 (synthesis of UA2)]

Using dicyclohexylmethane-4,4'-diisocyanate 5 mol as a diisocyanate, N-methyl-N-(2-hydroxyethyl)-4-hydroxybutanamine 1 mol as a diol and Amino acid amide was synthesized in the same manner as in Synthesis Example 1, except that 1.5 mol of polytetramethylene glycol and 5.4 mol of 2-hydroxyethyl acrylate of a mono(meth)acrylate containing a hydroxyl group were used. Formate UA2 (hereinafter referred to as "UA2").

[Example 1]

The active energy ray-curable resin composition was prepared at the blending ratio shown in Table 1. The resin composition was bar-coated and applied to a polycarbonate resin sheet (manufactured by SABIC Co., Ltd., trade name LEXAN LS-II) having a thickness of 253 mm, a width of 125 mm, and a thickness of 3 mm, so that the thickness of the cured coating film was 10 μm. on. Then, the organic solvent was volatilized by heat-treating the resin plate on which the coating film was formed in an oven at 60 ° C for 3 minutes. Thereafter, ultraviolet rays having a wavelength of 340 nm to 380 nm were irradiated to the coating film at a cumulative light amount of 3000 mJ/cm ² in the air using a high-pressure mercury lamp to cure the coating film, thereby obtaining a cured film.

Each of the above evaluations was performed on the resin molded article in which the cured film obtained in this manner was formed. The evaluation results are shown in Table 1. Further, the numerical values of the columns of the resin compositions in Tables 1 and 2 refer to parts by mass. Further, the abbreviations in Tables 1 and 2 refer to the compounds or products shown in Table 3.

[Example 2 to Example 10, Comparative Example 1 to Comparative Example 5]

A resin composition was prepared from the materials shown in Table 1 or Table 2 and the mixing ratio, and a resin molded article having a cured film formed thereon was obtained under the same conditions as in Example 1. The evaluation results are shown in Tables 1 and 2.

[summary of evaluation results]

As shown in Table 1, in the resin compositions of Examples 1 to 9, the blending ratio of the components (a) to (c) was within a predetermined range, and therefore the evaluation results were good. Although the resin composition of Example 10 is excellent in abrasion resistance, weather resistance, and heat resistance, the content of the component (c) is large, and thus the storage stability of the coating material is poor.

As shown in Table 2, in the resin composition of Comparative Example 1, since the content of the component (a) is large and the content of the component (b) is small, the weather resistance of the cured film is poor. In the resin compositions of Comparative Example 2 and Comparative Example 3, since the content of the component (a) is small, the cured film is resistant. Poor wear. In the resin composition of Comparative Example 4, since the content of the component (b) is small, the weather resistance of the cured film is poor. The resin composition of Comparative Example 5 does not contain the component (b) but contains the urethane urethane which is not the component (b) as the (meth)acrylic acid urethane, so that the storage stability of the coating is poor, and the hard coating is hardened. The weather resistance of the film is also poor.

[Industrial availability]

The cured film obtained from the resin composition of the present invention is effective for improving the weather resistance and abrasion resistance of resin molded articles such as various types of lamp fittings, window glass, and watch-type protective layers for automobiles.

Claims (17)

An active energy ray-curable resin composition comprising a radically polymerizable compound and a photopolymerizable initiator (d), and the radical polymerizable compound contains the following formula based on 100% by mass of the total amount ( 1) Polycaprolactone-modified mono- or polypentaerythritol poly(meth)acrylate (a) 57% by mass to 90% by mass and (meth)acrylic acid urethane (b) 10 The mass% to 43% by mass, the (meth)acrylic acid urethane is a polycarbonate polyol having a branched alkyl structure and having a number average molecular weight of 500 to 1000, and an alicyclic structure. Isocyanate, and a mono(meth)acrylate containing a hydroxyl group, In the formula (1), "4+2n" X are each independently a modified group of (meth)acryl oxime (which is (CH ₂ =CR-CO(O(CH ₂ ) ₅ C=O) _y -, The modified source itself is a lactone, R represents hydrogen or a methyl group, y represents an integer of 1 or more and 5 or less, (meth) propylene fluorenyloxy group (which is (CH ₂ =CR-COO-), and R represents hydrogen) Or a methyl group, or an -OH group, and at least one X is a modified group of (meth)acryl oxime, at least two X are (meth) propylene fluorenyl groups, and the remaining X is an -OH group; n is an integer from 0 to 4. The active energy ray-curable resin composition according to the first aspect of the invention, wherein the radical polymerizable compound is based on 100% by mass of the total amount, The radical polymerizable monomer (c) is 7% by mass or less, and the radical polymerizable monomer (c) is a poly(meth)acrylate (a) and the above (meth)acrylic acid in addition to the above mono or polypentaerythritol. A radically polymerizable monomer other than the urethane (b), which is crystallized at a temperature of 25 °C. The active energy ray-curable resin composition according to the first aspect of the invention, wherein the ultraviolet absorbing agent (e) is further contained in an amount of from 0.5 part by mass to 20 parts by mass per 100 parts by mass of the total amount of the radical polymerizable compound. . The active energy ray-curable resin composition according to the second aspect of the invention, wherein the ultraviolet absorbing agent (e) is further contained in an amount of from 0.5 part by mass to 20 parts by mass per 100 parts by mass of the total amount of the radical polymerizable compound. . The active energy ray-curable resin composition according to claim 3, wherein the ultraviolet ray absorbing agent (e) has a molecular weight of 500 or more. The active energy ray-curable resin composition according to claim 4, wherein the ultraviolet ray absorbing agent (e) has a molecular weight of 500 or more. The active energy ray-curable resin composition according to claim 3, wherein the ultraviolet absorbing agent (e) is a combination of two or more kinds of ultraviolet absorbing agents having a molecular weight of 500 or more. The active energy ray-curable resin composition according to claim 4, wherein the ultraviolet absorbing agent (e) is a combination of two or more ultraviolet absorbing agents having a molecular weight of 500 or more. The active energy ray-curable resin composition according to any one of claims 1 to 8, wherein the total amount of the radical polymerizable compound is 100 The mass part further contains 0.1 parts by mass to 5 parts by mass of the hindered amine light stabilizer (f). A resin molded article obtained by forming a hardened film on the surface thereof, which is obtained by curing the active energy ray-curable resin composition according to any one of claims 1 to 8. A resin molded article obtained by forming a hardened film on the surface thereof, which is obtained by curing the active energy ray-curable resin composition according to claim 9 of the patent application. The resin molded article according to claim 10, wherein the resin molded article is a headlamp for an automobile. The resin molded article according to claim 11, wherein the resin molded article is an automotive headlamp lens. The method for producing a resin molded article according to claim 10, wherein the active energy ray-curable resin composition according to any one of claims 1 to 8 is applied to a resin. The surface of the molded article is irradiated with the active energy ray of the obtained coating film. The method of producing a resin molded article according to claim 12, wherein the active energy ray-curable resin composition according to any one of claims 1 to 8 is applied to a resin. The surface of the molded article is irradiated with the active energy ray of the obtained coating film. The method for producing a resin molded article according to claim 11, wherein the active energy ray-curable resin composition according to claim 9 is applied to the surface of the resin molded article, and The obtained coating film irradiates the active energy ray. The method for producing a resin molded article according to claim 13, wherein the active energy ray-curable resin composition according to claim 9 is applied to the surface of the resin molded article. The obtained coating film irradiates the active energy ray.